JPH01108207A - Manufacture of modified olefin polymer - Google Patents

Abstract

PURPOSE:To prevent an olefin polymer from decomposing when modified, by cograft-polymerizing an olefin polymer in the form of particles using an unsaturated carboxylic acid or a derivative thereof and an unsaturated silane compound together. CONSTITUTION:An olefin polymer in the form of particles is brought into contact with an unsaturated carboxylic acid or a derivative thereof and an unsaturated silane compound in an inert gas in the substantial absence of a liquid medium, and they are cograft-polymerized at a temperature lower than the melting point of the above olefin polymer using a radical initiator. It is preferred that the unsaturated carboxylic acid or the derivative thereof be a compound represented by formula I or II (wherein R<1> and R<2> are each hydrogen or an aliphatic hydrocarbon group; and R<3> is hydrogen, an aliphatic hydrocarbon group or an aromatic hydrocarbon group). As the unsaturated silane compound, a compound represented by formula III, IV or V (wherein R<1> and R<2> are each an aliphatic saturated hydrocarbon group; m is 0, 1, 2, 3 or 4; n is 0, 1 or 2; p is 1, 2, 3, 4 or 5; and q is 0, 1, 2, 3 or 4) is preferred.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Technology] The present invention relates to a method for producing a modified olefin polymer having excellent adhesion to metals, glass, inorganic fillers, and polar resins such as polyvinyl alcohol.

[Conventional technology and its problems] Conventionally, olefin polymers have good mechanical properties, transparency,
Although it has good moldability, it has the disadvantage of poor adhesion to metals, glass, inorganic fillers, and polar resins because it is nonpolar. In order to compensate for these drawbacks, olefin polymers are modified with unsaturated carboxylic acids, their anhydrides, or their esters, such as acrylic acid, maleic acid, maleic anhydride, and methyl acrylate, or they are modified with vinyltrimethoxysilane. A method of modifying with a silane coupling agent such as silane coupling agent has been proposed.

However, although the adhesion of the modified olefin polymer obtained by this method to metals, glass, inorganic fillers, and polar resins is improved, the decomposition reaction of the olefin polymer occurs simultaneously during modification, so the melt flow There are drawbacks such as an increase in molding rate, making molding difficult, and a decrease in impact resistance.

Therefore, in order to prevent the decomposition of the olefin polymer, in JP-A-50-119,888, a specific hydroperoxide was blended as a graft initiator, and
A production method has been proposed in which maleic anhydride is graft-polymerized to a molten polyolefin at a temperature of
When polypropylene is used as a polyolefin, the melt flow rate increases and the decomposition of polypropylene is not sufficiently prevented. Methods for modifying with an unsaturated silane compound such as methoxysilane include a method in which the olefin polymer is heated at a temperature higher than the melting point temperature and graft polymerized in the presence of a radical initiator, or a method in which the olefin polymer is dissolved in a solvent. Two methods are known: post-graft polymerization in the presence of a radical initiator, but these methods require a subsequent granulation or powdering step.

However, when olefin polymerization is used in powder or granular form, such as when manufacturing composite materials by mixing olefin polymers with powders made of inorganic or organic materials such as glass, calcium carbonate, carbon, talc, and wood flour, There are many
In the above method, the powder is not produced in the form of powder, which is extremely disadvantageous in terms of industrial production.

In addition to the above two methods, there is a method of graft polymerizing an olefin polymer in the form of particles by adding an olefin polymer and an unsaturated carboxylic acid, its anhydride or its ester, or vinyl There is a method of graft polymerization by suspending an unsaturated silane compound such as trimethoxysilane and a radical initiator, but this method has the disadvantage that the generation of the graft polymer is suppressed by chain transfer of the solvent to the growing graft polymer radical. .

Furthermore, in JP-A-50-77-493, a powdery olefin polymer is brought into contact with maleic anhydride in the substantial absence of a liquid medium, and radicals are generated at a temperature lower than the melting temperature of the olefin polymer. A method of graft polymerization using an initiator has been proposed, but it has the drawback that the melt flow rate of the modified olefin polymer increases.

As a result of research on the above problem, the present inventors found that decomposition of the olefin polymer can be prevented by co-graft polymerization using a combination of an unsaturated carboxylic acid or its derivative and an unsaturated silane compound as grafting monomers. However, we have arrived at the present invention.

[Means for Solving the Problems] The present invention provides a method for producing an olefin polymer for the purpose of further improving the adhesion of the olefin polymer to metals, glass, inorganic fillers, and polar resins. , in an inert gas, in the substantial absence of a liquid medium, a particulate olefin polymer, an unsaturated carboxylic acid or a derivative thereof, and an unsaturated silane compound are brought into contact with each other, and the temperature is lower than the melting temperature of the olefin polymer. This method of producing a modified olefin polymer is characterized in that decomposition reaction of the olefin polymer is prevented during modification by co-graft polymerization using a radical initiator at a low temperature.

The olefin polymers used in the present invention include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-1-butene homopolymers, copolymers copolymerized with other α-olefins, and other α-olefins. An olefin polymer mixture blended with a olefin polymer is used.

In the present invention, it is important that these polymers are in a state where they are not melted or dissolved in a solvent, that is, the shape of these polymers is granular or powdery.
A diameter of 4+sm, preferably 0.05 to 2 mm is good.

Examples of unsaturated carboxylic acids or derivatives thereof used in the present invention include acrylic acid, methacrylic acid, maleic acid,
Fumaric acid, itaconic acid, ethyl acrylate, methyl acrylate, acrylamide, ethyl methacrylate, methacrylamide, maleic acid monoethyl ester, maleic acid diethyl ester, maleic acid monoamide, maleic acid diamide, maleimide, N-phenylmaleimide, anhydrous Maleic acid etc. are used.

Particularly preferred are compounds represented by the general formula: and compounds represented by the general formula (where nl and n2 are hydrogen or an aliphatic hydrocarbon group, H3 is an aliphatic hydrocarbon group or an aromatic hydrocarbon group) ), which represents a hydrogen group.

Specifically, for example, maleic anhydride, maleimide, N-
Phenylmaleimide and the like are used. What is the proportion of unsaturated carboxylic acid or its derivatives used?

It is usually used in an amount of 0.1 to 50% by weight, preferably 1 to 20% by weight, based on the olefin polymer.

The unsaturated silane compound used in the present invention has the general formula R
91RnY-η (where R is an ethylenically unsaturated hydrocarbon group, an alkoxy group or a 70oxy group, R is an aliphatic saturated hydrocarbon group, Y is a hydrolyzable organic group, n
represents 0.1 or 2), specifically, R is vinyl, allyl, impropenyl, butenyl, cyclohexenyl, cyclopentagenyl, γ-methacryloxypropyl, styryl, β -styrylethyl, etc., where R is methyl, ethyl, propyl, decyl, etc., and Y is a group such as methoxy, ethoxy, butoxy, formyloxy, acetoxy, propionyloxy, alkyl or arylamino.

Particularly preferred are compounds represented by the general formula: %formula%(3), compounds represented by the general formula; %formula%(4), or compounds represented by the general formula (provided that in the above general formula, nl, R2 is an aliphatic saturated hydrocarbon group, m is 0, 1, 2.3 or 4, and n is 0.
1 or 2, p is 1, 2, 3.4 or 5, q is 0, 1
, 2.3 or 4) Specifically, for example, vinyltrimethoxysilane, allyltrimethoxysilane,
γ-methacryloxypropyltrimethoxysilane, p-
Styryltrimethoxysilane, β-styrylethyltrimethoxysilane, etc. are used. The ratio of unsaturated silane compound used is usually 0.1 to 50% relative to the olefin polymer.
% by weight, preferably 2-30% by weight.

As the radical initiator used in the present invention, various peroxides or azo compounds can be used.
For example, benzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, azobisisobutyronitrile, etc. are used. The proportion of the radical initiator used is usually 0.01 to 20% by weight, preferably 0.2 to 10% by weight, based on the olefin polymer.

The reaction temperature may be lower than the temperature at which the olefin polymer melts, but in order to increase the grafting rate, it is better to be relatively high. Usually 50 to 170 °C, preferably 7
It is preferable to carry out the process at a temperature of 0 to 150°C.

The reaction system is conducted in an inert gas such as nitrogen or argon in the substantial absence of a liquid medium.

However, since maleic anhydride, phosphoric acid, maleimide, etc. used in the present invention are sublimable, the maleic anhydride is stored in low-temperature parts attached to the reactor, such as a pressure gauge attached to the top of the reactor and a stirrer. Crystals such as acid and maleimide may precipitate and inhibit the continuation of the reaction. In such a case, it is preferable to use a small amount of a solvent that becomes gaseous at a relatively low temperature, such as benzene, toluene, acetone, etc., to prevent the formation of crystals such as maleic anhydride and maleimide.

The order of addition of the components to be used is not particularly limited as long as the powdery polyolefin polymer, unsaturated carboxylic acid or its derivative, unsaturated silane compound, and radical initiator are brought into contact with each other simultaneously.

After completing one polymerization, in order to remove unreacted unsaturated carboxylic acid or its derivative, unsaturated silane compound, radical initiator, and unnecessary polymer of unsaturated carboxylic acid or its derivative and unsaturated silane compound. It is preferable to wash with a solvent; examples of the solvent include a solvent in which an unsaturated carboxylic acid or its derivative, an unsaturated silane compound, a radical initiator, a polymer of an unsaturated carboxylic acid or its derivative and an unsaturated silane compound are dissolved; For example, toluene, acetone, methyl ethyl ketone, tetrahydrofuran, etc. are used.

[Effects of the Invention] The polyolefin composition produced according to the present invention improves the adhesion of polyolefin to metals such as iron and aluminum, glass, and polar resins such as polyvinyl alcohol, nylon, and saponified ethylene-vinyl acetate copolymers. is achieved.

Moreover, it is possible to prevent the decomposition reaction of the polyolefin that occurs together with the graft copolymerization that occurs in conventional methods, and there are advantages such as being able to prevent molding difficulties and deterioration of impact resistance due to an increase in melt a-rate.

[Example] Next, Examples and Comparative Examples will be shown.
MFR) was measured according to JIS K 7210, and Izot impact strength (notched) was measured according to JIS K 7110. The content of unsaturated carboxylic acid or its derivative in the modified olefin polymer was determined by infrared absorption spectrum.

The content of the solenoid polymer in the modified olefin polymer was determined using fluorescent X-rays. Furthermore, the content of the unsaturated carboxylic acid or its derivative and the unsaturated silane compound graft-polymerized to the solenoid polymer in the modified olefin polymer can be determined by dissolving the modified olefin polymer in acetone after completely dissolving it in a solvent. By precipitating the unsaturated carboxylic acid or its derivative in the acetone, the unsaturated carboxylic acid or its derivative that has not been graft-polymerized to the olefin hair polymer and the unsaturated silane compound are completely dissolved in acetone, and the unsaturated carboxylic acid or its derivative in the acetone insoluble matter is completely dissolved. The amount was determined by infrared absorption spectrum, and the unsaturated silane compound was fixed by fluorescent X-rays.

Example-1 Polypropylene powder (M F R
=30) After adding 500g and completely replacing with nitrogen gas, 80g of maleic anhydride, IQg of benzoyl peroxide,
and toluene 501 were inserted. After heating the inside of the system to 90°C, 90g of vinyltrimethoxysilane was press-injected and
The reaction was carried out at ℃ for 5 hours while stirring.

After the reaction was completed, the product was thoroughly washed with acetone and then dried under reduced pressure. Yield of modified olefin polymer: 540g
The MFR was 1.0. The contents of maleic anhydride and vinyltrimethoxysilane in the modified olefin polymer were 2.7% by weight and 4.3% by weight. Furthermore, maleic anhydride grafted to polypropylene in the modified olefin polymer The contents of vinyltrimethoxysilane were 1.6% by weight and 2.1% by weight.

Example-2 50g of N-phenylmaleimide as unsaturated carboxylic acid
The same procedure as in Example 1 was conducted except that 70 g of γ-methacryloxypropyltrimethoxysilane was used as the unsaturated silane compound. The yield of modified olefin polymer is 550
g, and the MFR was 4.1. The content of N-phenylmaleimide and γ-methacryloxypropyltrimethoxysilane in the modified olefin polymer is 3.2% by weight,
It was 8.0% by weight.

Furthermore, the content of polypropylene hegegrafted N-phenylmaleimide and γ-methacryloxypropyltrimethoxysilane in the modified olefin polymer was 1.5% by weight.
, 2.2% by weight.

Example-3 50 g of maleic anhydride as unsaturated carboxylic acid, 70 g of β-styrylethyltrimethoxysilane as unsaturated silane compound, 7 g of dicumyl peroxide as radical initiator
The same procedure as in Example 1 was carried out except that the reaction temperature was 120°C. The yield of modified olefin polymer is 51?
0g, and the MFR was 2.4. The contents of maleic anhydride and β-styrylethyltrimethoxysilane in the modified olefin polymer were 3.1% by weight and 7.3% by weight.

Furthermore, the content of polypropylene hegegrafted maleic anhydride and β-styrylethyltrimethoxysilane in the modified olefin polymer was 1.4% by weight and 3.5% by weight.
Met.

Comparative Example 1 The same procedure as Example 2 was carried out except that 5000 ml of toluene was used as the solvent. The modified olefin polymer yield is
The weight was 510 g, and the MFR was 30. The contents of maleic anhydride and vinyltrimethoxysilane in the modified olefin ffi combination were 0.88% by weight and 1.1% by weight.

Furthermore, the contents of maleic anhydride and vinyltrimethoxysilane grafted onto polypropylene in the modified olefin polymer were 20% by weight and 0.31% by weight.

Comparative Example 2 The same procedure as Example 1 was carried out except that polypropylene (MFR=1.8) was used and maleic anhydride was not used. The yield of modified reflex polymer was 520 g, and M
FR was 2.7. The vinyltrimethoxysilane content in the modified olefin polymer was 3.8% by weight.

Further, the content of vinyltrimethoxysilane grafted to polypropylene in the modified olefin polymer was 1.7% by weight.

Comparative Example 3 The same procedure as Example 1 was carried out except that polypropylene (MFR=1.8) was used and vinyltrimethoxysilane was not used. Yield of modified olefin polymer is 500g
The MFR was 5.3.

The content of maleic anhydride in the modified olefin polymer is 0.
．． It was 1 layer weight %.

Furthermore, the content of maleic anhydride grafted onto polypropylene in the modified olefin polymer was 0.10% by weight.

Example-4 Modified polyolefin 99 obtained in Examples-1 to -3
．． 8% by weight, 2.6-di-butyl-cresol, and 60.1% by weight of calcium stearate were thoroughly mixed using a Henschel mixer (trade name). These mixtures were molded into test pieces using an extruder set at a temperature of 230°C, and the Izod impact strength was measured. The results are shown in Table 1.

Comparative Example-4 Modified polyolefin 99 obtained in Comparative Examples-1 to -3
．． 8 fl volume %, 2.8-di-butyl-cresol, and 60.1 weight % calcium stearate were thoroughly mixed using a Henschel mixer (trade name). These mixtures were molded into test pieces using an extruder set at a temperature of 230°C, and the Izod impact strength was measured. The results are shown in Table 1.

Comparative Example-5 38.8% by weight of the polyolefin used in Examples-1 to -3 and Comparative Examples-1 to -3, 2.6-di-butyl-
Cresol, calcium stearate 0.1 fl each (3
1% was thoroughly mixed using a Henschel mixer (trade name). These mixtures were molded into test pieces using an extruder set at a temperature of 230°C, and the Izod impact strength was measured. The results are shown in Table 1.

Example-5 Modified polyolefin 30 obtained in Examples-1 to -3
jl (1%, propylene-ethylene coffi combination (MF
R3,0 engineering tyrene 8% by weight) 89.8% by weight 2.8-
Di-butyl-cresol, calcium stearate each O
, t were mixed into pellets using a Henschel mixer (trade name) and an extruder. This pellet is 230
C
A sheet of JJ was manufactured.

Next, a steel plate with a thickness of 300 mm (JIS G31415PC
G-SB) was degreased using trichlorethylene. The obtained polyolefin sheet (A) and steel plate (B) were
Three layers were stacked in the order of A-B, heated and pressed using a compression molding machine at a bonding temperature of 220° C. and a pressure of 20 atm for 1 minute, and then cooled to create a composite board. The T-peel strength of this composite plate was measured according to JIS 8854. The results are shown in Table 2.

Comparative Example-6 Modified polyolefin 30 obtained in Comparative Examples-1 to -3
fi i%, propylene-ethylene copolymer (MFR3
, 0 engineering tyrene 8% by weight) 89.8% by weight and 2.6-
Di-butyl-cresol, calcium stearate 60
．． 1% by weight was kneaded into pellets using a Henschel mixer (trade name) and an extruder. Below, examples-
The same procedure as in step 5 was carried out. The results are shown in Table 2.' Comparative Example-7 30% by weight of the polyolefin used in Examples-1 to -3 and Comparative Examples-1 to -3, propylene L/7-ethylene copolymer (MFR 3,0 engineering) 8% by weight of tyrene) f19.8
% by weight, 2.8-di-butyl-cresol, and 60.1% by weight of calcium stearate were kneaded into pellets using a Henschel mixer (trade name) and an extruder. Hereinafter, Example 5 was carried out in the same manner. The results are shown in Table 2.

Example-6 Modified polyolefin 30 obtained in Examples-1 to -3
rabbit amount%, propylene-ethylene copolymer (M F R3
, 0 engineering tyrene 8% by weight) SL8% by weight and 2.6-di-
Butyl-cresol, calcium stearate) each 0.1
were kneaded into pellets using a Henschel mixer (trade name) and an extruder.

This pellet was supplied to a T-gui film manufacturing apparatus at 230° C. to manufacture a film having a thickness of 50 IL.

The obtained polyolefin film (A) and 20 g of ethylene-vinyl acetate copolymer film (Kuraray Eval Film EF-F) (B) were stacked in three layers in the order of A-B-A, and a heat sealing device was used. and bonding temperature 200
The mixture was heated and pressurized for 1 second at a temperature of 1 at. The edges of the two layers, the ethylene-vinyl acetate copolymer film and the modified polyolefin film, which are in contact with the surface on which the adhesive peel strength of this composite film is to be measured, are held in the chuck of an Autograph manufactured by Shimabara Manufacturing Co., Ltd., and the peeling speed is set at 50 cm/min. The stress detected below was measured and defined as peel strength. The results are shown in Table 2.

Comparative Example-8 Modified polyolefin 30 obtained in Comparative Examples-1 to -3
Weight%, propylene-ethylene copolymer (MFR3,0
(89.8% by weight) and 2.6-di-
Butyl-cresol, calcium stearate 60.1
% by weight was mixed into pellets using a Henschel mixer (trade name) and an extruder. The following steps were carried out in the same manner as in Example-6. The results are shown in Table 2.

Comparative Example-9 Polyolefin used in Comparative Examples-1 to -3 and Comparative M-1 to -3 30% by weight, propylene-ethylene copolymer (MFR 3.0 polyethylene 8%) 69.8 layer weight% and 2,6-di-butyl-cresol and 60.1% by weight of calcium stearate were kneaded using a Henschel mixer (trade name) and an extruder to form pellets.

The following steps were carried out in the same manner as in Example-6. The results are shown in Table 2.

Manual continuation supplementary book September 30, 1986

Claims (3)

[Claims] (1) in an inert gas and in the substantial absence of a liquid medium,
It is characterized in that a powdery olefin polymer, an unsaturated carboxylic acid or its derivative, and an unsaturated silane compound are brought into contact with each other, and co-graft polymerization is carried out using a radical initiator at a temperature lower than the melting temperature of the olefin polymer. Method for producing modified olefin polymer. (2) Unsaturated carboxylic acid or its derivative has a general formula; ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) A compound represented by the general formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) At least one selected from the group consisting of compounds represented by
2. The method of claim 1, wherein the compound is a species compound. (However, in the above general formula, R^1 and R^2 represent hydrogen or an aliphatic hydrocarbon group, and R^3 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group.) (3) The unsaturated silane compound has the general formula; CH2=CH■CH_2■_mSiR^1 (OR^2)
3＿＿−＿n...Compound or general formula shown in (3); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(4) Compounds or general formula shown in (4); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...( 5) At least one selected from the group consisting of the compounds shown in
2. The method of claim 1, wherein the compound is a species compound. (However, in the above general formula, R^1, R^2 are aliphatic saturated hydrocarbon groups, m is 0, 1, 2, 3 or 4, n is 0, 1 or 2, p is 1, 2, 3 , 4 or 5, q is 0
, 1, 2, 3 or 4. )(4) Claim 1 in which the olefin polymer is homopolypropylene and a copolymer of propylene and an olefin other than propylene
The method described in section.